Hydrolyzed starch compositions and their use in food applications

ABSTRACT

Provided herein are common starch-based and waxy starch-based hydrolyzed starches. The hydrolyzed starches described herein demonstrate desirable properties over existing hydrolyzed starches for food applications, including but not limited to, dairy, ready-to-eat cereal coatings, clean-label confectionary products, nutritional and cereal bars, crumb chocolate, infant and/or elderly nutrition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application62/469,780, filed on Mar. 10, 2017, which is hereby incorporated byreference.

TECHNICAL FIELD

This disclosure relates to hydrolyzed starches, the process formanufacturing hydrolyzed starches, and their use in food applications.

BACKGROUND

Starch is a common food ingredient used in both food and non-foodapplications. Hydrolyzed starches are the dried products or aqueousdispersions of saccharides (hydrolysates) obtained by hydrolysis ofnative starch by using suitable acid or enzymes. Certain such hydrolyzedstarches may be referred to as “maltodextrins.” They are typicallycategorized having a dextrose equivalent (DE) of less than 20. DE isdefined as the percentage of reducing sugar calculated as dextrose on adry weight basis. Hydrolyzed starches are desirable for foodapplications because they extend the technical use of starch in manyfood and non-food applications. Hydrolyzed starches offer uniquefunctional properties in food, label-friendly options, superior mouthfeel and taste, and cost effectiveness when compared to otherhydrocolloid systems.

BRIEF SUMMARY

Provided herein are common starch-based and waxy starch-based hydrolyzedstarches having a range of DE values, such as 1, 5, 10, and 18. Thehydrolyzed starches described herein are obtained through an enzymatichydrolysis technique using, for example, alpha-amylases such as DSM'sMaxamyl™ HT Ultra. In some aspects, the hydrolyzed starches describedherein demonstrate desirable properties over certain hydrolyzed starchesof the prior art for food applications, such as, but not limited to,dairy, ready-to-eat cereal coatings, clean-label confectionary products,nutritional and cereal bars, crumb chocolate, infant nutrition, and/orelderly nutrition.

DETAILED DESCRIPTION Hydrolyzed Starch Compositions

To obtain the hydrolyzed starches of the present invention a variety ofstarting starch materials can be used. In certain aspects, the startingstarch materials may be corn/maize starch, potato starch, tapiocastarch, pulse starch (including but not limited to pea starch), and ricestarch. Other suitable starting starch materials may be sweet potatostarch, wheat starch, mung bean starch, oat and barley starch. Suchstarting starch materials may come from regular starch crops or mutantstarch crops. Regular starch, also known as “non-mutant” or “common”starch, is made up of two components—amylose and amylopectin, whichrange from 20-30% and 70-80%, respectively, of the total starch. Amyloseis mainly a linear polymer consisting of α-(1→4) linked D-Glucopyranosylunits, whereas amylopectin is a branched polymer consisting of linearα-(1→4) linked D-Glucopyranosyl units with α-(1→6) linkedD-Glucopyranosyl branch chains. Distinguishable from common starch,mutant starch varieties known in the art may include waxy type or highamylose type hybrids. Waxy starches are made primarily (nearly 100%) ofan amylopectin component whereas high amylose mutants typically containa high content of amylose, usually upwards of 40% amylose. Certain suchmutant starch varieties are known in the art and may be derived fromdifferent botanical sources such as, corn, potato, wheat, barley,tapioca, etc.

Utilizing the methods described herein, a variety of hydrolyzed starchcompositions, derived from waxy and/or common starch materials, may beachieved, which demonstrate superior performance over hydrolyzedstarches of the prior art.

The hydrolyzed starches described herein are of various dextroseequivalent (DE) values ranging from 0 to 20, such as, for example,DE0-3, DE3-8, DE8-14, or DE14-20, and DE 1, DE 5, DE 10, and DE 18. Thehydrolyzed starches may be derived from waxy and/or common starch. Insome aspects, the hydrolyzed starches are derived from waxy corn starchand/or or common corn starch. In some aspects, the hydrolyzed starchesdescribed herein have desirable gelling properties. In some aspects, thehydrolyzed starches described herein have reduced viscosity, which mayallow for easier and more efficient in-process handling, dispensing, andpumping. In some aspects, the hydrolyzed starches described herein havean opaque clarity. In some such aspects, the hydrolyzed starchesdescribed herein may be particularly useful in dairy food applications.In some aspects, the hydrolyzed starches described herein have reducedmolecular weights compared to prior art hydrolyzed starches. In somesuch aspects, the hydrolyzed starches described herein are more easilydigestible, and may be particularly useful in infant and elderlynutrition.

Exemplary Waxy Starch-Based Hydrolyzed Starches

In some aspects, a hydrolyzed starch composition provided herein isderived from waxy starch. In some aspects, the hydrolyzed starchcomposition is obtained from waxy starch using an alpha-amylase such asDSM's Maxamyl™ HT Ultra. In some aspects, such a hydrolyzed starchcomposition derived from waxy starch has a dextrose equivalent (DEvalue) of greater than 0 to 3, such as 0.5 to 3, or 1 to 2, or about1.5. In some aspects, the hydrolyzed starch composition with a DE valueof greater than 0 to 3 (i) has a degree of polymerization (DP) between46-6172 of >80%, and/or (ii) has an average molecular weight (mw) of<500 kDa, and/or (iii) forms a gel at 30% solids in aqueous medium. Insome aspects, the hydrolyzed starch composition has a degree ofpolymerization (DP) between 46-6172 of 80-95%. In some aspects, thehydrolyzed starch composition has an opaque clarity indicated by aHunter L value of >30, >40, >50, >60, >70, or >80. In some aspects, thehydrolyzed starch composition has an opaque clarity indicated by aHunter L value of 30-100, or 40-100, or 50-100, or 60-100, or 70-100. Insome aspects, the hydrolyzed starch composition has a gel strength at30% solids in aqueous medium of >300 g, >400 g, >500 g, >600 g, >700 g,or >800 g, or 300-2000 g, or 500-2000 g, or 500-1500 g. In some aspects,the hydrolyzed starch has a lower average molecular weight than ahydrolyzed starch with a similar DE produced by hydrolyzing waxy starchwith α-amylase GC100 (Genencor). In some instances, a hydrolyzed starchwith a similar DE produced by hydrolyzing waxy starch with α-amylaseGC100 does not form a gel at 30% solids in aqueous medium.

In some aspects, a hydrolyzed starch composition derived from waxystarch has a dextrose equivalent (DE value) of 3 to 9, such as 4 to 9,or 5 to 9, or 6 to 9, or 7 to 9. In some aspects, the hydrolyzed starchcomposition with a DE value of 3 to 9 (i) has a degree of polymerization(DP) between 10-45 of >40%, and/or (ii) an average molecular weight (mw)of <60 kDa. In some aspects, the DP of hydrolyzed starch between 10-45is >50%, or >60%, or 40-95%, 40-90%, 50-90%, 55-90%, 60-90%, 60-80%. Insome aspects, the average mw of the hydrolyzed starch is <50 kDa, or <40kDa. In some aspects, the hydrolyzed starch composition forms a gel at30% solids in aqueous medium. In some aspects, the composition has anopaque clarity indicated by a Hunter L value of >30, >40, >50, >60, >70,or 30-90, 40-90, 50-90, or 60-90. In some aspects, the hydrolyzed starchcomposition is obtained from waxy starch using an alpha-amylase such asDSM's Maxamyl™ HT Ultra. In some aspects, the hydrolyzed starch has alower average molecular weight and/or a higher percentage of hydrolyzedstarches with a DP between 10-45 than a hydrolyzed starch with a similarDE produced by hydrolyzing waxy starch with α-amylase GC100 (Genencor).In some aspects, a hydrolyzed starch with a similar DE produced byhydrolyzing waxy starch with α-amylase GC100 does not form a gel at 30%solids in aqueous medium.

In some aspects, a hydrolyzed starch composition derived from waxystarch has a dextrose equivalent (DE value) of 9 to 14, or 9 to 13. Insome aspects, the hydrolyzed starch composition with a DE of 9 to 14 (i)has a degree of polymerization (DP) between 10-45 of >40%, and/or (ii)an average molecular weight (mw) of <35 kDa. In some aspects, the DP ofthe hydrolyzed starch between 10-45 is >50% or >60%. In some aspects,the DP of the hydrolyzed starch between 10-45 is 40-95%, 50-95%, or60-95%. In some aspects, the average mw of the hydrolyzed starch is <30kDa, <25 kDa, <20 kDa, or 2-20 kDa, 5-20 kDa, or 5-15 kDa. In someaspects, the hydrolyzed starch composition is obtained from waxy starchusing an alpha-amylase such as DSM's Maxamyl™ HT Ultra. In some aspects,the hydrolyzed starch has a lower average molecular weight and/or ahigher percentage of hydrolyzed starches with a DP between 10-45 than ahydrolyzed starch with a similar DE produced by hydrolyzing waxy starchwith α-amylase GC100.

In some aspects, a hydrolyzed starch composition derived from waxystarch has a dextrose equivalent (DE value) of 14 to 20, or 16 to 20. Insome aspects, the hydrolyzed starch composition with a DE of 14 to 20(i) has a degree of polymerization (DP) between 6-45 of >60%, and/or(ii) an average molecular weight (mw) of <10 kDa. In some aspects, thehydrolyzed starch has an average mw of <8 kDa, <7 kDa, <6 kDa, 1-10 kDa,1-8 kDa, 1-7 kDa, or 1-6 kDa. In some aspects, the hydrolyzed starch hasa DP between 6-45 of >70%, >80%, 60-95%, 70-95%, or 80-95%. In someaspects, the hydrolyzed starch has a DP between 1-45 of >80% or >90%, or80-99%, or 90-99%. In some aspects, the hydrolyzed starch composition isobtained from waxy starch using an alpha-amylase such as DSM's Maxamyl™HT Ultra. In some aspects, the hydrolyzed starch has a lower averagemolecular weight and/or a higher percentage of hydrolyzed starches witha DP between 1-45 than a hydrolyzed starch with a similar DE produced byhydrolyzing waxy starch with α-amylase GC100. In some aspects, the waxystarch is waxy corn starch.

In various aspects, the hydrolyzed starch may be derived from cornstarch, potato starch, tapioca starch, pea starch, legume starch, orrich starch.

Exemplary Common Starch-Based Hydrolyzed Starches

In some aspects, a hydrolyzed starch composition provided herein isderived from common starch. In some aspects, the hydrolyzed starchcomposition is obtained from common starch using an alpha-amylase suchas DSM's Maxamyl™ HT Ultra. In some aspects, such a hydrolyzed starchcomposition derived from common starch has a dextrose equivalent (DEvalue) of greater than 0 to 3, such as 0.5 to 3, or 1 to 2, or about1.5. In some aspects, the hydrolyzed starch composition with a DE valueof greater than 0 to 3 (i) has a degree of polymerization (DP) between601-6172 of >40%, and/or (ii) has an average molecular weight (mw) of<3500 kDa. In some aspects, the hydrolyzed starch has a DP between601-6172 of 40-70% and an average mw of 1000-3500 kDa. In some aspects,the hydrolyzed starch composition has a viscosity of >1000 cp, or1000-2000 cp, or >1200 cp, or 1200-2000 cp, at 95° C. at 200 s⁻¹. Insome aspects, the hydrolyzed starch composition has a viscosity of >3000cp, >4000 cp, or >5000 cp, or 3000-8000 cp, 4000-8000 cp, or 5000-8000cp, at 50° C. at 200 s⁻¹. In some aspects, the hydrolyzed starch with aDP between 601-6172 is >45%, or 45-70%. In some aspects, the hydrolyzedstarch has a lower average molecular weight and/or a higher percentageof hydrolyzed starches with a DP between 601-6172 than a hydrolyzedstarch with a similar DE produced by hydrolyzing common starch withα-amylase GC100 (Genencor).

In some aspects, a hydrolyzed starch composition derived from commonstarch has a dextrose equivalent (DE value) of 3 to 8, such as 3 to 6 or4 to 6. In some aspects, the hydrolyzed starch composition with a DEvalue of 3 to 8 (i) has a degree of polymerization (DP) between 10-125of >20%, and/or (ii) has an average molecular weight (mw) of <300 kDa.In some aspects, the DP of the hydrolyzed starch is between 10-125is >30%, >40%, or >50%, or 20-80%, 30-80%, 40-80%, or 50-80%. In someaspects, the average mw of the hydrolyzed starch is <200 kDa, or 20-300kDa, or 20-200 kDa, or 20-150 kDa. In some aspects, the hydrolyzedstarch composition forms a gel at 30% solids with a viscosity of <10 cpat 95° C. at 200 s⁻¹, and/or <40 cp or 15-40 cp at 50° C. at 200 s⁻¹,and/or <100 cp or 40-100 cp or 40-90 cp at 20° C. at 1000 s⁻¹. In someaspects, the hydrolyzed starch has a lower average molecular weightand/or a higher percentage of hydrolyzed starches with a DP between10-125 than a hydrolyzed starch with a similar DE produced byhydrolyzing common starch with α-amylase GC100. In some aspects, thehydrolyzed starch forms a gel with a lower viscosity than a hydrolyzedstarch with a similar DE produced by hydrolyzing common starch withα-amylase GC100.

In some aspects, a hydrolyzed starch composition derived from commonstarch has a dextrose equivalent (DE value) of 8 to 14, such as 8 to 12.In some aspects, the hydrolyzed starch composition with a DE value of 8to 14 (i) has a degree of polymerization (DP) between 10-125 of >30%,and/or (ii) has an average molecular weight (mw) of <40 kDa. In someaspects, the DP between 10-125 is >40%, >50%, >60%, or >70%, or 30-95%,40-95%, 50-95%, 60-95%. In some aspects, the average mw of thehydrolyzed starch is <30 kDa, or 5-40 kDa, or 5-30 kDa. In some aspects,the hydrolyzed starch composition forms a gel at 30% solids in aqueousmedium. In some aspects, the hydrolyzed starch composition has an opaqueclarity indicated by a Hunter L value of >50, >60, >70, or >80, or50-100, 60-100, 70-100, 80-100, or 85-99. In some aspects, thehydrolyzed starch has a lower average molecular weight and/or a higherpercentage of hydrolyzed starches with a DP between 10-125 than ahydrolyzed starch with a similar DE produced by hydrolyzing commonstarch with α-amylase GC100.

In some aspects, a hydrolyzed starch composition derived from commonstarch has a dextrose equivalent (DE value) of 14 to 20, such as 15 to20 or 16 to 20. In some aspects, the hydrolyzed starch composition witha DE value of 14 to 20 has an average molecular weight (mw) of <20 kDaor <10 kDa, or 1-15 kDa, or 1-12 kDa, or 1-10 kDa, or 2-10 kDa. In someaspects, the composition has an opaque clarity indicated by a Hunter Lvalue of >50, or >60, or 50-90, or 50-80, or 60-80. In some aspects, thehydrolyzed starch has a lower average molecular weight than a hydrolyzedstarch with a similar DE produced by hydrolyzing common starch withα-amylase GC100.

In various aspects, the hydrolyzed starch may be derived from cornstarch, potato starch, tapioca starch, pea starch, legume starch, orrich starch. In some aspects, the common starch of the hydrolyzed starchcomposition is common corn starch.

Process for Manufacturing Hydrolyzed Starch

One skilled in the art will appreciate that the commercial production ofhydrolyzed starches includes the steps of (1) liquefaction(gelatinization or solubilization of starch); (2) saccharification(hydrolysis, specific DE attainment); (3) clarification (removal ofinsoluble); (4) optionally refining using a carbon column or ionexchange resin; (5) evaporation to increase solids concentration; and(6) liquid hydrolyzed starch load-out or spray drying. A more detaileddescription of an exemplary process for making the hydrolyzed starchcompositions provided herein may be found in the Examples section.

There are many ways to complete the hydrolysis step. The hydrolyzedstarch compositions described herein may be achieved, for example,through an enzymatic hydrolysis techniques utilizing alpha-amylases suchas DSM's Maxamyl™ HT Ultra.

Potential End-Use Applications

The various aspects of hydrolyzed starch compositions described hereincan be used in a variety of food applications, including but not limitedto, dairy, ready-to-eat cereal coatings, clean-label confectionaryproducts, nutritional and cereal bars, crumb chocolate, infantnutrition, and/or elderly nutrition.

In some aspects, a hydrolyzed starch composition provided herein is usedin dairy applications. Nonlimiting exemplary such dairy applicationsinclude yogurt and sour cream. In some aspects, a hydrolyzed starchcomposition provided herein having a DE of >0 to 3 is particularlysuitable for such dairy applications. Some such hydrolyzed starchesprovided herein have high viscosity at both higher and lower temperatureand shear, making them particularly suitable for dairy applications,such as dairy applications involving homogenization. For example, sourcream made using a 1DE common starch-derived hydrolyzed starch describedherein demonstrated good structure and a smooth, shiny appearancecompared to sour cream made using a control 1DE common starch-derivedhydrolyzed starch, which had weaker structure. Similarly, yogurt madeusing a 1DE common starch-derived hydrolyzed starch described hereindemonstrated good body and texture, while yogurt made using a control1DE common starch-derived hydrolyzed starch had too think body andunacceptable texture.

Certain hydrolyzed starches provided herein comprise lower degrees ofpolymerization and/or lower average molecular weight than currentlyavailable hydrolyzed starches. Such characteristics make the hydrolyzedstarch more easily digestible, and thus, more suitable for infant and/orelderly nutrition. For example, hydrolyzed starches described hereinwith higher DE values have lower molecular weights and are thusparticularly suitable for infant and/or elderly nutrition.

Examples Example 1: Analytical Methods L*a*b* Hunter Color:

Thirty percent solutions were made of each composition by mixingstirring and heating to the point of boiling, stirring again and boilinga second time before adding back lost water. Aliquots of the solutions(18-19 g of solution) were placed on 2′A inch petri dishes to obtainL*a*b* values. Samples were grouped by treatment type and by startingmaterial composition. Hunter L*a*b* values were obtained by placing thepetri dish on a large sampling port (2¼ inch diameter) and covered by anopaque cup. Clear samples were shown as dark (low L value) and opaquewhite samples were shown as white (high L* value).

Viscosity and Gel Strength Characterization:

The hydrolyzed starch samples were prepared by dispersing anywhere from10% to 50% dry solids into cold deionized water, followed by heating andmixing to form a dispersion free of lumps. This hot solution was pouredinto the cup and bob viscometer which was equilibrated at 50° C.

Viscosity measurements were made using an Anton Paar MCR 502. Geometryused was cup and bob CC27. A shear rate of 200 1/s was used to monitorthe sample as it was heated from 50° C. up to 95° C. No sampledeformation was performed as the sample was cooled from 95° C. to 20° C.over the course of 38 min. When the sample cooled to 20° C. a shear ratescan from 0.1 1/s to 1000 1/s was run. The thermal profile of the scanstarted at 50° C. for 5 minutes and heated to 95° C. in a 23 minuteinterval and continued monitoring viscosity for 5 minutes at 95° C. Thesample was cooled from 95° C. down to 20° C. over the course of 38minutes and was held at 20° C. for 5 minutes prior to a shear rate scanstarting at 0.1 1/s and proceeding to 1000 1/s over the course of 7minutes.

The above aqueous preparations were used for gel strength measurementsusing a TAXT2 texture analyzer from Stable Micro Systems. The aqueoussamples after viscosity measurements were refrigerated (˜5° C.±2° C.)for 4 days in sealed container. After 4 days of storage, the sampleswere removed from the refrigerator and equilibrated to room temperature(22° C.). The gel strength measurements were performed at roomtemperature.

The instrument is equipped with a 5 Kg load cell, which is calibratedwith a 2.5 Kg weight. Texture evaluation is done using the TAXT2 textureanalyzer equipped with a stainless steel ½ inch diameter round nosefinger probe. The parameters used are listed below:

Test Mode and Option: Measure Force in Compression; Return to Start

Parameters:

-   -   Pre Test Speed: 4.00 mm/sec    -   Test Speed: 2.00 mm/sec    -   Post Test Speed: 4.00 mm/sec    -   Rupture Test Dist.: 4.0 mm    -   Distance: 10.0 mm    -   Force: 100.0 g    -   Time: 5.00 sec.    -   Count: 5    -   Load Cell: 5 Kg    -   Temperature: 25° C.

Trigger:

-   -   Type: Auto    -   Force: 5.0 g

Essentially, the probe approaches the sample at 4 mm/sec until thesurface is detected with a 5 g trigger force, then data acquisitionstarts. From the trigger point the probe continues at a reduced 2 mm/sectravelling 10 mm (1 cm) into the sample. The probe then reverses. Thevial is held down to prevent the probe from lifting the vial when itreturns to its starting position at 4 mm/sec.

The maximum resistance in grams of force is the value reported for gelstrength.

Absolute Molecular Weight, DP Distribution, and Radius of Gyration:

Absolute molecular weight was characterized by size exclusionchromatography using an Alliance 2690 HPLC (high performance liquidchromatography) system, manufactured by Waters Corporation, Milford,Mass., coupled to a DAWN HELEOS II multi-angle light scattering (MALS)instrument, manufactured by Wyatt Technology, Santa Barbara, Calif., anda 2410 refractive index detector manufactured by Waters Corporation,Milford, Mass. Waters Corporation Styragel columns HR5 and HR4,connected in series, were used to separate the sample components. Thecolumn temperature was controlled at 60° C. and the sample compartmenttemperature was set to 40° C. The internal temperature of the refractiveindex detector was set to 40° C. The HPLC mobile phase, 50 mM lithiumbromide in 90% dimethyl sulfoxide (DMSO) in water, flow rate was set to0.4 mL/min and the total run time was 90 minutes. Waters CorporationEmpower 3 software was used to control the Alliance 2690 HPLC and 2410refractive index detector, and Wyatt Technology Astra 6.1 software wasused to collect the light scattering and refractive index signals andperform the data analysis for calculating DP distribution and radius ofgyration. Samples solutions were prepared by dispersing 200 mg of driedhydrolyzed starch product in mobile phase (50 mM lithium bromide in 90%DMSO in water). The solutions were uniformly dispersed by stirring for 1hour at room temperature, boiling and stirring for 10 minutes, and thenstirring overnight at room temperature. The final step was to filter thesolutions, using a 1 um PTFE syringe filter disk, into a 2 mL HPLC vial.

Polydispersity:

Polydispersity is the ratio of weight average molecular weight (Mw) tonumber average molecular weight (Mn).

Example 2: Experimental Hydrolyzed Starch Prototypes

This pilot process included traditional starch liquefaction whichutilized jet cooker and spray dryer equipment. The liquefactionvariables, including enzyme dosage, pH, aqueous slurry temperature andliquefaction hold time, were adjusted to result in target dextroseequivalent, DE, in the final product. Experimental prototypes were madeusing DSM's alpha-amylase enzyme Maxamyl™ HT Ultra. The controlthermostable liquid alpha amylase, GC100, which is produced fromBacillus Licheniformis and supplied by Danisco US Inc., and Liquozyme®SC DS, a thermostable alpha amylase supplied by Novozymes Inc, were usedto make alternative prototypes that are compared to the experimentalprototypes.

Experimental hydrolyzed starch prototypes were made targeting DE of 1-2,5, 10, and 18 for both native common and native waxy corn starch.Approximately 30 lbs was targeted for each prototype to undergoapplication and analytical testing. Due to capacity and throughputlimits on the jet cooker, multiple trial runs were conducted to producethe full 30 lbs needed for each experimental DE. In all, eight sets ofexperimental prototypes were produced. The experimental prototypesproduced with native common corn starch resulted in the following DE's:0.81/0.63/0.80, 4.67/5.26, 9.04/10.80 and 19.1/16.3. These DE's matchedsatisfactorily with the target DE's of 1-2, 5, 10, and 18, respectively.Similarly, the experimental prototypes produced with native waxy cornstarch resulted in the following DE's: 0.44/1.49, 8.40/8.05, 9.53/12.05,and 19.78/16.7. These DE's matched satisfactorily with the target DE'sof 1-2, 5, 10, and 18, respectively.

In addition to the experimental prototypes, control prototypes wereproduced using GC100 α-amylase enzyme. Four control prototypes wereproduced targeting DE's of 1-2, 5, and 18. The control prototypesproduced from native common corn starch resulted in the following DE's:1.43/0.96, 5.55/5.26, and 19.2/18.0, which matched satisfactorily withthe target DE's of 1-2, 5, and 18. The control prototype produced withnative waxy corn starch resulted in DE's of 21.26/17.8, which matchedsatisfactorily with the target DE of 18. Commercial products and controlprototypes made with the GC100 α-amylase were used as controls tocompare to experimental prototypes.

Example 3: Process for Making Hydrolyzed Starch Prototypes

Materials: The starting base for the experimental prototypes includedCargill Gel 04230, Batch#01215CHYAA, a native waxy corn starch andCargill Gel 03420, Batch#02415CHYBB, a native common corn starch. DSM'salpha-amylase enzyme Maxamyl™ HT Ultra was used to make the hydrolyzedstarch prototypes and an α-amylase was used as a control enzyme. HCl(1:1) and NaOH (50% w/w concentration) were used.

Chemical Analysis: The moisture content of dried prototypes wasdetermined using a gravimetric moisture meter. Dextrose Equivalent (DE)analysis was performed on both in-process liquid and final driedsamples. The dried hydrolyzed starches of 1 DE and 5 DE values weretested for DE based on Schrool's titration method, which determinesreducing sugars in the hydrolyzed starches by reaction with a stabilizedalkaline solution of a copper salt. When reaction conditions (i.e.,time, temperature, reagent concentration, and composition) arecontrolled, the amount of copper reduced is proportional to the amountof reducing sugars in the sample analyzed. In the current DE method, thereducing sugar concentration (expressed as dextrose) is estimated byiodometric determination of the unreduced copper remaining afterreaction.

Schrool's titration method: Weigh 5.0 g (dry basis) of sample, place itin a 200 mL Kohlrausch flask, and dilute to volume with warm deionizedwater. Shake the flask to ensure the sample dispersion is free of clumpsof dried hydrolyzed starch. Transfer the contents of the flask to a 250mL beaker. Pipet 20.0 mL of the sample dispersion into a 250 mLErlenmeyer flask and add 20.0 mL of freshly prepared Schoorl's solution(10 mL each of Fehling's Solution A and B, available from SigmaAldrich). Add 10.0 mL of deionized water to the flask. Add glass beadsto the flask to prevent bumping during the next steps of boiling. Coverthe mouth of the flask. Prepare a blank containing 20.0 mL of Schoorl'sSolution and 30.0 mL of deionized water. Place both flasks on a hotplate (400° C.) and bring to a boil in about three minutes. Continueboiling for two minutes and then cool quickly to room temperature usinga 50° F. water bath or in the sink under cold running water. Add 10.0 mLof 30% KI solution and then add 10.0 mL of 30% H2SO4 solution. Titrateimmediately with 0.1 N Na2S2O3 solution. Near the endpoint (appearanceof a milky color), add starch indicator and titrate until the bluestarch-iodine color is discharged.

Calculation of DE value: Subtract the sample titer from the blank titer.Find the Reducing Sugar content (Dextrose Equivalent) as below:

${\% \mspace{14mu} {Reducing}\mspace{14mu} {Sugar}\mspace{14mu} \left( {{dry}\mspace{14mu} {basis}} \right)} = {\frac{{mg}\mspace{14mu} {Dextrose}\mspace{14mu} \left( {{from}\mspace{14mu} {Table}} \right) \times 200\mspace{14mu} {mL} \times 100\%}{{Sample}\mspace{14mu} {{Wt}.{of}}\mspace{14mu} 5\mspace{14mu} g\mspace{14mu} \left( {{dry}\mspace{14mu} {basis}} \right) \times 20\mspace{14mu} {mL} \times 1000} = \frac{{mg}\mspace{14mu} {Dextrose}}{{Sample}\mspace{14mu} {{Wt}.\left( {{dry}\mspace{14mu} {basis}} \right)}}}$

For the higher DE hydrolyzed starch powders, such as DE 10 and DE 18samples, an FTIR (Fourier Transform Infrared Spectroscopy) method wasused. The FTIR instrument analyzes by measuring the reflectance of asample at a specific wavelength in the mid-infrared region of theelectromagnetic spectrum. The instrument is calibrated using the samplesof known DE prior to the tests.

Liquefaction Method: The liquefaction process consisted of jet cookingof aqueous starch slurry (concentration range from 12-30% dry solids inthe presence of DSM's alpha-amylase enzyme Maxamyl™ HT Ultra, a starchhydrolyzing enzyme). To jet cook aqueous starch slurry, the slurry waspumped at a fixed rate through a direct injection steam heater. Directsteam injection generates high temperature (95° C.-130° C.) and shearthat converts starch slurry into starch paste. Starch paste was thenpumped through a flash chamber (reducing temperature instantaneously toabout 90° C.), and then it is finally collected into a product tankequipped with a cover and an agitator.

The cooking temperature during jet cooking step was targeted between110-120° C. After the jet cooking step, liquefied starch in the producttank was held at 90° C. until a desired degree of hydrolysis inliquefact is achieved. The product was then spray dried. Below is astep-wise procedure that was followed for this starch liquefactionprocess:

1. Starch slurry preparation: In a mixing tank (feed tank), prepare 25%(w/w starch solids) starch slurry in water using 10 Kg starch(commercial base). Add required quantity of water in the mixing tankfirst, and then turn on mixing at a slow speed. Slowly add the entirequantity of starch to the mixing tank while contents are mixedcontinuously at a slow speed. Maintain slurry at ambient temperature.Adjust speed of mixing to prevent settling of starch solids. Allowstarch to hydrate for a minimum of 15 minutes.

2. pH adjustment & preparing for enzyme conversion: Check pH and thetemperature of the slurry in feed tank. Adjust pH to 4.8-5.2 using 1:1HCl acid buffer. Record quantity of acid buffer used. After pHadjustment, continue mixing of the slurry at a gentle speed. Weigh therequired quantity of enzyme in a clean plastic container and add enzymeinto the slurry. Five minutes after adding the enzyme, check the pH andthe temperature of the slurry once again. Continue mixing.

3. Jet Cooking Step: Using water as the feed for the jet cooker toprepare jet cooker and equilibrate the cooking temperature between110-117° C. and outlet temperature of 95° C. (atmospheric flash inproduct tank). Once the cooking conditions are set, start feeding thestarch slurry into the jet cooker. Record this time as time 0 bystarting a stop watch. Keep the stop watch running until the completionof step#3 and #4 to record total liquefaction time. Continue mixing ofthe slurry while the slurry is being pumped through jet cooker. Recordthe time that the liquefact starts to come out of the jet-cooker output;this is the residence time of liquefact in jet cooker piping. Collectliquefact into product tank equipped with overhead mixer and temperaturecontrol up to 95° C.

4. Holding Liquefact at 95° C.: Hold liquefact in product tank at 95° C.for a desired holding time that corresponds to a DE (extent ofhydrolysis) value desired in final products. Continue mixing theliquefact at a slow speed. Total liquefaction times are recorded.

5. Enzyme Kill Step: Immediately after completion of desired holdingtimes (step 4 above), adjust pH to 2.7-3.0 at 95° C. and hold for 15minutes. Continue mixing the liquefact at a slow speed. To ensurecomplete inactivation of enzyme, temperature is controlled and holdingtime is 15 minutes.

6. Adjust pH between to 4.5±0.5. Continue mixing of liquefact. Adjust pHto 4.5±0.5 in liquefact using NaOH base buffer. Then, immediately draw aliquid sample for DE measurement. The starch liquefact is released forspray drying.

7. Cool and Dilute: Immediately after completion of pH adjustment, letthe slurry cool down to 55-60° C. (use cooling water circulation ifneeded). If desired prototype is in the 1-2 DE range, heating is notturned off because low-DE products will thicken quickly and make furtherprocessing difficult. Before spray drying a product with a 1-2 DE range,dilute to approximately 15% DS, to allow the product to be transferredto spray dryer through peristaltic pump.

Spray Drying Method: A Niro spray dryer was used for drying the starchliquefact. Below is a step-wise procedure of spray drying that wasfollowed in the current study.

1. Ensure liquefact prepared by jet cooker is stored in product tank at50-65° C. while continuously stirring the contents at slow speed toprevent stratification.

2. Transfer approximately 10 to 15 L of hot liquefact (at 50-65° C.)from product tank to a 5 gallon white plastic pail. Immerse this plasticpail into a 60° C. water bath. Set an overhead mixer to continuously mixthe contents in the pail at a slow speed. Record % solids in theliquefact using moisture meter. As needed, adjust % solids in liquefactto lower level using sanitized water to ensure optimum spray dryingoperation.

3. Feed deionized water into the spray dryer to equilibrate the inlettemperature of the dryer to approximately 200° C. and the outlettemperature to approximately 100° C.

4. Switch the feed from water to liquefaction. Monitor both the inletand outlet temperatures.

5. Record feed rate, inlet and outlet temperatures of spray dryer.Collect ˜15 lbs of dried product, and store in air tight packaging.Record the final weight and % moisture of the dried product.

Example 4: Characteristics of Experimental Hydrolyzed Starch Prototypes

This process created eight experimental hydrolyzed starches and fourcontrol hydrolyzed starches. Table 1 lists the prototypes and theirfinal dried weights. Table 2 lists the control prototypes and theirfinal dried weights.

TABLE 1 Target Final Amnt Dried Total Starch Type DE Trial DE Product(lbs) Amnt (lbs) Native Common 1-2 DE   #1 0.81 11.60 42.60 NativeCommon  #2 0.63 14.80 Native Common  #3 0.80 16.20 Native Common  5 DE #5 4.67 15.80 34.60 Native Common  #6 5.26 18.80 Native Common 10 DE #7 9.04 17.40 33.51 Native Common  #8 10.80 16.11 Native Common 18 DE#10 19.1 16.20 31.17 Native Common #5 P-1 16.3 14.97 Native Waxy 1-2 DE #12 0.44 16.58 31.63 Native Waxy #13 1.49 15.05 Native Waxy  5 DE #148.40 17.55 34.30 Native Waxy #15 8.05 16.75 Native Waxy 10 DE #16 9.5317.41 35.94 Native Waxy #17 12.05 18.53 Native Waxy 18 DE #18 19.7816.54 34.54 Native Waxy #7 P-1 16.7 18.00 Pea Starch  1 DE #31 0.55 5.685.68

TABLE 2 Dried Product Combined Starch Type Enzyme Target DE Trial FinalDE (lbs) Total (lbs) Native Waxy GC100 18 DE  #20 21.65 15.98 34.36Native Waxy GC100 #11 P-1 17.8 18.38 Native Common GC100 5 DE #24 5.5516.89 34.07 Native Common GC100 #25 5.26 17.18 Native Common GC100 18DE  #26 19.2 15.28 33.25 Native Common GC100 #10 P-1 18.0 17.97 NativeCommon GC100 1 DE #28 1.43 14.52 31.46 Native Common GC100 #29 0.9616.94 Pea Starch GC 100 1 DE #32 2.19 7.42 7.42 Native Waxy Liquozyme 5DE #30 7.82 10.71 10.71 Control Hydrolyzed starch samples that arecommercial available from Cargill Manufacturing Plants Cargill Dry 01909GC 100 10 DE  — 11.4 — — (Native Common) Cargill Dry 01960 GC 100 10 DE — 11.80 — — (Waxy corn starch) Cargill Dry 01901 GC 100 1-2 DE  — 1.5 —— (Waxy corn starch) Cargill Dry 01956 GC 100 5 DE — 8.2 — — (Waxy cornstarch)

Results: 1 DE Waxy Starch-Based Hydrolyzed Starch

Table 3 and 4 demonstrate the analytical properties of 1 DE waxystarch-based hydrolyzed starches discussed above. Tables 3 and 4 showthe properties of 1 DE experimental hydrolyzed starch made using thealpha amylase derived from Pseudomonas fluorescens Biovar I and 1DEcontrol hydrolyzed starch made using GC100 alpha amylase.

1 DE experimental hydrolyzed starch formed milky white dispersionscompared to clear, transparent dispersions formed by control hydrolyzedstarch. 1 DE experimental hydrolyzed starch showed lower averagemolecular weight (386 KDa) vs control hydrolyzed starch made using GC100(709 KDa). 1 DE experimental hydrolyzed starch showed gelling at 30%solids in aqueous medium vs control hydrolyzed starch made using GC100,which showed no gel formation. 1 DE experimental hydrolyzed starch alsoshowed gelling at 20% solids in aqueous medium. 1 DE experimentalhydrolyzed starch showed lower viscosity as a function of temperatureand shear compared to control hydrolyzed starch made using GC100. Thelower in-use process viscosity enables easier and more efficientin-process handling, dispensing and pumping. In some aspects, this mayalso enable higher solids handling at higher temperature/shearconditions compared to control hydrolyzed starch.

TABLE 3 1 DE Waxy hydrolyzed starch CTRL 1901 Average M. Wt (Da) EXP #13Exp# 12 (Cargill Dry 01901) DP range From to (1.49 DE) (0.44 DE) (1.5DE) DP 1-5 0 909 0 0 0 DP 6-9 909 1,557 0 0 0 DP 10-19 1,557 3,177 0 0 0DP 20-45 3,177 7,389 0 0 2.29 DP 46-125 7,389 20,349 15.97 0 7.79 DP126-280 20,349 45,459 15.47 0 9.68 DP 281-600 45,459 97,299 14.58 012.02 DP 601-1500 97,299 243,828 18.56 0 16.11 DP 1500-3075 243,828500,000 14.31 30.14 15.03 DP 3075-6172 500,000 1,000,000 11.25 18.5414.59 DP 6172-7716 1,000,000 1,250,000 2.55 5.06 4.2 DP 7716-92591,250,000 1,500,000 1.69 4.09 3.2 DP 9259-10802 1,500,000 1,750,000 1.253.46 2.5 DP 10802-12346 1,750,000 2,000,000 0.86 2.97 2.09 DP12346-15432 2,000,000 2,500,000 1.07 4.89 3.05 DP 15342-18518 2,500,0003,000,000 0.62 3.93 2.13 >DP 18518 >3,000,000 1.82 26.92 5.34 DE 1.490.44 1.5 Polydispersity 7 3 12 (Rz, nm) 26 47 24 Average M. Wt (Kda) 3862464 709

TABLE 4 CTRL EXP #13 EXP # 12 (1901) (1.49 DE) (0.44 DE) (1.5 DE) GelFormation @ 30% YES — NO Gel Strength (g) (30% solids) 1000 — 0 GelStrength (g) (50% solids) Not tested — Not tested Viscosity (cp) at 95 Cat 200 s⁻¹ 16.7 89.45 26.8 Viscosity (cp) at 50 C at 200 s⁻¹ 54.7 326.991.3 Viscosity (cp) at 20 C at 1000 s⁻¹ 199 960.9 340 Viscosity (cp) at20 C at 100 s⁻¹ 209 1346 365 Clarity (Scores) Opaque Opaque TransparentL*a*b* Hunter Color L* 89.38 — L* 11.41 a* −1.31 a* −0.86 b* 4.52 b*−5.1

Results: 5 DE Waxy Starch-Based Hydrolyzed Starch

Tables 5, 6, and 7 demonstrate the analytical properties of 5 DE waxystarch-based hydrolyzed starches discussed above. Tables 6 and 7 showthe properties of 5 DE experimental hydrolyzed starch made using thealpha amylase derived from Pseudomonas fluorescens Biovar I and 5 DEcontrol hydrolyzed starch made using GC100 alpha amylase. Table 5 showsthe properties of the 5 DE experimental hydrolyzed starch made using thealpha amylase derived from Pseudomonas fluorescens Biovar I and the 5 DEcontrol hydrolyzed starch made using Liquozyme® alpha amylase.

5 DE experimental hydrolyzed starch formed milky white dispersioncompared to clear/transparent dispersion formed by control hydrolyzedstarch (CNTRL 1956) made using GC100 alpha amylase. 5 DE experimentalhydrolyzed starch demonstrated lower average molecular weight (35 KDa or17 kDa) vs control hydrolyzed starch made using GC100 alpha amylase (75KDa) or control hydrolyzed starch made using Liquozyme® (85 KDa). % DEexperimental hydrolyzed starch showed gelling at 30% solids in aqueousmedium versus control hydrolyzed starch made using GC100 alpha amylase,which showed no gel formation. 5 DE experimental hydrolyzed starchshowed lower viscosity as a function of temperature and shear comparedto control hydrolyzed starch made using GC100 alpha amylase, and 5 DEexperimental hydrolyzed starch showed a different oligosaccharidecomposition compared to Control hydrolyzed starch.

TABLE 5 5 DE WAXY HYDROLYZED STARCH % Abundance EXP # 14 Liquozyme (8.40EXP # 30 DP range DE) (7.82 DE) 1-5 0 0 6-9 0 0 10-19 34.93 27.49 20-4533.05 7.59  46-125 17.79 14.35 126-280 5.62 15.83 281-600 3.18 12.96 601-1500 2.36 12.07 >1500 3.07 9.71 DE 8.4 7.82 Polydispersity 9 14(Mw/Mn) Radius of 18 11 Gyration (Rz, nm) Av M · Wt (Kda) 35 84

TABLE 6 5 DE WAXY HYDROLYZED STARCH % Abundance CTRL 1956 (Cargill EXP#Dry EXP # 14 15 (8.05 01956) DP range (8.40 DE) DE) (8.2 DE) 1-5 0 0.950 6-9 0 4.03 10.84 10-19 34.93 34.69 18.63 20-45 33.05 31.85 6.43 46-125 17.79 17.67 11.31 126-280 5.62 6 16.27 281-600 3.18 2.95 14.15 601-1500 2.36 1.4 13.53 >1500 3.07 0.47 8.84 DE 8.4 8.05 8.2Polydispersity 9 5 16 (Mw/Mn) Radius of Gyration 18 15 <10 (Rz, nm) Av M· Wt (Kda) 35 17 75

TABLE 7 Liquozyme EXP # 14 EXP # 15 EXP # 30 CTRL 1956 (DE 8.40) (DE8.05) (7.82 DE) (DE 8.2) Gel Formation Yes — Yes N Gel Strength (g) (30%solids) 3 — 0 0 Gel Strength (g) (40% solids) 179 — 10 0 Gel Strength(g) (50% solids) 1689 — 200 1724 Viscosity (cp) at 95 C. at 200 s⁻¹ 2.82.35 — 4.8 Viscosity (cp) at 50 C. at 200 s⁻¹ 6.8 5.37 Not tested 12.3Viscosity (cp) at 20 C. at 1000 s⁻¹ 16.4 12.54 Not tested 36.6 Viscosity(cp) at 20 C. at 100 s⁻¹ 18.2 13.53 Not tested 34.4 Clarity (Scores)Opaque Opaque Opaque Transparent L*a*b* Hunter Color L* 77.39 — L* 3.16a* −1.51 a* −0.01 b* 9.73 Not tested b* −0.58

Results: 10 DE Waxy Starch-Based Hydrolyzed Starch

Tables 8 and 9 demonstrate the analytical properties of 10 DE waxystarch-based hydrolyzed starches discussed above. Specifically, Tables 8and 9 shows the properties of 10 DE experimental hydrolyzed starch madeusing the alpha amylase derived from Pseudomonas fluorescens Biovar Iand 10DE control hydrolyzed starch made using GC100 alpha amylase.

10 DE experimental hydrolyzed starch formed milky white dispersionscompared to clear, transparent dispersions formed by control hydrolyzedstarch. 10 DE experimental hydrolyzed starch showed lower averagemolecular weight (11 kDa and 7 kDa) vs control hydrolyzed starch (44KDa). 10 DE experimental hydrolyzed starch showed gelling at 30% solidsin aqueous medium vs control hydrolyzed starch, which showed no gelformation. 10 DE experimental hydrolyzed starch showed lower viscosityas a function of temperature and shear compared to the controlhydrolyzed starch.

10 DE experimental hydrolyzed starch showed different oligosaccharidecomposition compared to the control hydrolyzed starch made using GC100alpha amylase. 10 DE experimental hydrolyzed starch contained only about1% (by wt) oligosaccharide fractions that are higher than DP 601 whereasthe control hydrolyzed starch made using GC100 alpha amylasecontained >13% by wt of oligosaccharide compositions that are higherthan DP 601. In some aspects, the 10 DE experimental hydrolyzed starchmay be useful for infant or elderly nutrition where low molecular weighthydrolyzed starches are desired.

TABLE 8 10 DE WAXY HYDROLYZED STARCH % Abundance EXP # EXP CTRL 1960 16#17 (Cargill Dry (9.53 (12.05 01960) DP range DE) DE) (11.8 DE) 1-5 0 09.81 6-9 7.26 4.53 17.83 10-19 31.16 53.46 12.85 20-45 34.78 29.74 6.51 46-125 18.67 8.35 12.43 126-280 4.96 1.78 16.33 281-600 2.14 0.95 11.87 601-1500 0.77 1.19 8.84 >1500 0.26 0 3.53 DE 9.5 12.05 11.8Polydispersity 3 3 17 (Mw/Mn) Radius of Gyration 12 <10 <10 (Rz, nm) AvM · Wt (Kda) 11 7 44

TABLE 9 EXP # 17 CTRL EXP #16 (12.05 (1960) (9.53 DE) DE) (11.8 DE) GelFormation Yes — NO Gel Strength (g) (30% solids) 7 — 0 Gel Strength (g)(50% solids) 362 — 0 Viscosity (cp) at 95 C. at 200 s⁻¹ 2.4 2.29 3.5Viscosity (cp) at 50 C. at 200 s⁻¹ 5.6 4.39 8.5 Viscosity (cp) at 20 C.at 1000 s⁻¹ 15.4 11.66 23.9 Viscosity (cp) at 20 C. at 100 s⁻¹ 13.4 10.121.8 Clarity (Scores) Opaque — Transparent L*a*b* Hunter Color L* 71.25— L* 3.26 a* −1.23 a* −0.11 b* 8.09 b* −0.71

Results: 18 DE Waxy Starch-Based Hydrolyzed Starch

Tables 10 and 11 demonstrate the analytical properties of 18 DE waxystarch-based hydrolyzed starches discussed above. Specifically, Tables10 and 11 shows the properties of 18 DE experimental hydrolyzed starchmade using the alpha amylase derived from Pseudomonas fluorescens BiovarI and 18DE control hydrolyzed starch made using GC100 alpha amylase.

18 DE experimental hydrolyzed starch formed milky white dispersionscompared to clear, transparent dispersions formed by control hydrolyzedstarch made using GC100. 18 DE experimental hydrolyzed starch showedlower average molecular weight (4 Da) vs control hydrolyzed starch madeusing GC100 (16 KDa). 18 DE experimental hydrolyzed starch had adifferent oligosaccharide composition compared to control hydrolyzedstarch. 18 DE experimental hydrolyzed starch contained less than 1% (bywt) oligosaccharide fractions that are higher than DP 601, whereas thecontrol hydrolyzed starch made using GC100 contained >4% by wt ofoligosaccharide compositions that are higher than DP 601. In someaspects, the 18 DE experimental hydrolyzed starch may be useful forinfant or elderly nutrition where low molecular weight hydrolyzedstarches are desired.

TABLE 10 18 DE WAXY HYDROLYZED STARCH % Abundance EXP # 18 CTRL GC 100(19.78 #7 (Phase I) (Phase I - #11) DP range DE) (16.7 DE) (17.8 DE) 1-515.01 7.81 19.58 6-9 19.24 24.22 33.22 10-19 43.97 41.65 5.82 20-4518.79 20.34 6.93  46-125 1.79 4.05 14.74 126-280 0.71 0.7 12.3 281-6000.48 0.32 5.29  601-1500 0 0.91 1.54 >1500 0 0 0.57 DE 19.7 16.7 18Polydispersity 2 3 13 (Mw/Mn) Radius of Gyration <10 <10 17 (Rz, nm) AvM · Wt (Kda) 4 4 16

TABLE 11 EXP # 7 CTRL EXP # 18 P-1 GC 100 (19.78 DE) (16.7 DE) (17.8 DE)Gel Formation NO — NO Gel Strength (g) (30% solids) 0 — 0 Gel Strength(g) (50% solids) 0 — 0 Viscosity (cp) at 95 C. at 200 s⁻¹ 2.06 2.16 2.16Viscosity (cp) at 50 C. at 200 s⁻¹ 3.35 3.76 3.67 Viscosity (cp) at 20C. at 1000 s⁻¹ 11.3 11.53 11.3 Viscosity (cp) at 20 C. at 100 s⁻¹ 7.158.22 7.7 Clarity (Scores) Clear Clear Clear L*a*b* Hunter Color L* 27.65L* 25.39 a* −1.38 a* −1.36 b* −2.1 b* −1.24

Results: 1 DE Common Starch-Based Hydrolyzed Starch

Tables 12 and 13 demonstrate the analytical properties of 1 DE commonstarch-based hydrolyzed starches discussed above.

1 DE experimental hydrolyzed starch showed lower average molecularweight (2835 KDa and 2108 kDa) vs control hydrolyzed starch (4078 KDa).Despite the lower average molecular weight, the experimental hydrolyzedstarch formed gels with similar strength and showed higher viscosity asa function of shear and temperatures compared to the control. 1 DEexperimental hydrolyzed starch showed higher viscosities at 25 to 95°C., demonstrating higher shear and temperature tolerance compared to thecontrol hydrolyzed starch.

TABLE 12 1 DE common hydrolyzed starch EXP #1 Average M. Wt (Da) (0.81EXP # 2 Control # 29 DP range From to DE) (0.63 DE) (0.96 DE) DP 1-5 0909 0 0 0 DP 6-9 909 1,557 0 0 0 DP 10-19 1,557 3,177 0 0 0 DP 20-453,177 7,389 0 0 0 DP 46-125 7,389 20,349 0 0 0 DP 126-280 20,349 45,4590 0 0 DP 281-600 45,459 97,299 0 0 0 DP 601-1500 97,299 243,828 24.3 0 0DP 1500-3075 243,828 500,000 21.16 29.95 0 DP 3075-6172 500,0001,000,000 11.93 17.54 29.06 DP 6172-7716 1,000,000 1,250,000 3.38 5.565.54 DP 7716-9259 1,250,000 1,500,000 2.75 3.48 5.68 DP 9259-108021,500,000 1,750,000 2.4 2.81 5.89 DP 10802-12346 1,750,000 2,000,0002.06 2.43 3.48 DP 12346-15432 2,000,000 2,500,000 3.6 4.08 4.81 DP15342-18518 2,500,000 3,000,000 2.99 3.34 3.96 > DP 18518 >3,000,00025.44 30.82 41.57 DE 0.6 0.81 0.96 Polydispersity 4 5 3 (Rz, nm) 53 4362 Average M. Wt (Kda) 2835 2108 4078

TABLE 13 1 DE COMMON HYDROLYZED STARCH EXP #2 EXP# 1 CTRL #29 (0.81 DE)(0.63 DE) (0.96 DE) Gel Formation YES — YES Gel Strength (g) (30%solids) 2600 — 2700 Gel Strength (g) (50% solids) Not — Not measuredmeasured Viscosity (cp) at 95 C. at 200 s⁻¹ 1629 1657  797 Viscosity(cp) at 50 C. at 200 s⁻¹ 6780 6584 2710 Viscosity (cp) at 20 C. at 1000s⁻¹ 2350 2509  753 Viscosity (cp) at 20 C. at 100 s⁻¹ 8510 9084 1210Clarity (Scores) Opaque Opaque Opaque L*a*b* Hunter Color L* 88.07 — L*88.33 a* −2.68 a* −2.31 b* 5.43 b* 5.84

Results: 5 DE Common Starch-Based Hydrolyzed Starch

Tables 14 and 15 demonstrate the analytical properties of 5 DE commonstarch-based hydrolyzed starches discussed above.

5 DE experimental hydrolyzed starch showed lower average molecularweight (117 KDa and 56 kDa) vs control (592 KDa). Despite the loweraverage molecular weight, the 5 DE experimental hydrolyzed starch formedgels that showed stronger strength than that of control hydrolyzedstarch gels. 5 DE experimental hydrolyzed starch demonstrated lowerviscosities than that of control hydrolyzed starch samples when measuredat a range of temperatures (20° C. to 95° C.) and shear rates (100 s⁻¹ t100 s⁻¹).

TABLE 14 5 DE COMMON HYDROLYZED STARCH % Abundance EXP EXP #5 #6 (4.67(5.26 CTRL #25 DP range DE) DE) (5.26 DE) 1-5 0 0 0 6-9 0 0 0 10-19 016.74 0 20-45 32.15 27.19 0  46-125 31.22 25.00 7.49 126-280 12.94 11.7520.23 281-600 9.89 9.01 26.33  601-1500 7.81 6.94 15.65 >1500 5.99 3.3730.3 DE 4.67 5.26 5.3 Polydispersity 11 8 10 (Rz, nm) 32 24 39 AverageM. Wt (Kda) 117 56 592

TABLE 15 EXP #5 EXP# 6 CTRL #25 (4.67 DE) (5.26 DE) (5.55 DE) GelFormation YES — YES Gel Strength (g) (30% solids) 400 — 160 Gel Strength(g) (50% solids) Not — Not measured measured Viscosity (cp) at 95 C. at200 s⁻¹ 9 7.39 16.8 Viscosity (cp) at 50 C. at 200 s⁻¹ 27.7 20.67 58.7Viscosity (cp) at 20 C. at 1000 s⁻¹ 72 56.26 147 Viscosity (cp) at 20 C.at 100 s⁻¹ 165 109.16 201 Clarity (Scores) Opaque Opaque Opaque L*a*b*Hunter Color L* 94.2 — L* 88.82 a* −1.45 a* −2.82 b* 6.36 b* 5.75

Results: 10 DE Common Starch-Based Hydrolyzed Starch

Tables 16 and 17 demonstrate the analytical properties of 10 DE commonstarch-based hydrolyzed starches discussed above.

10 DE experimental hydrolyzed starch showed lower average molecularweight (12 KDa and 18 kDa) vs control hydrolyzed starch (59 KDa).Despite the lower average molecular weight, 10 DE experimentalhydrolyzed starch formed soft gels compared to no gel formation by thecontrol hydrolyzed starch samples. 10 DE experimental hydrolyzed starchdemonstrated lower viscosities than that of control hydrolyzed starchsamples when measured at a range of temperatures (20° C. to 95° C.) andshear rates (100 s⁻¹ to 100 s⁻¹). 10 DE experimental hydrolyzed starchformed opaque, milky white dispersions compared to the clear dispersionsformed by the control hydrolyzed starch samples.

TABLE 16 10 DE COMMON HYDROLYZED STARCH % Abundance CTRL 1909 EXP # 8(Cargill Dry (10.80 EXP #7 01909) DP range DE) (9.04 DE) (11.4 DE) 1-55.27 0 10 6-9 7.24 3.73 13.13 10-19 32.97 39.69 17.95 20-45 31.79 29.146.55  46-125 14.37 15.29 9.26 126-280 4.4 6.08 13.66 281-600 2.35 3.3111.76  601-1500 1.02 1.76 11.07 >1500 0.58 1.01 6.61 DE 10.8 9.04 11.4Polydispersity 4 5 23 (Rz, nm) 19 21 <10 Average M. Wt (Kda) 12 18 59

TABLE 17 10 DE COMMON HYDROLYZED STARCH CTRL 1909 (Cargill Dry EXP # 8EXP # 7 01909) (10.80 DE) (9.04 DE) (11.4 DE) Gel Formation YES — NO GelStrength (g) (30% solids) 39 — 0 Gel Strength (g) (50% solids) — — —Viscosity (cp) at 95 C. at 200 s⁻¹ 3.3 5.09 3.7 Viscosity (cp) at 50 C.at 200 s⁻¹ 8.4 11.18 9.2 Viscosity (cp) at 20 C. at 20.1 27.24 26.6 1000s⁻¹ Viscosity (cp) at 20 C. at 100 s⁻¹ 28.8 49.44 23.8 Clarity OpaqueOpaque Clear L*a*b* Hunter Color L* 90.75 — L* 3.2 a* −1.32 a* −0.06 b*7.21 b* −0.65

Results: 18 DE Common Starch-Based Hydrolyzed Starch

Tables 18 and 19 demonstrate the analytical properties of 18 DE commonstarch-based hydrolyzed starch discussed above.

18 DE experimental hydrolyzed starch showed lower average molecularweight (7 KDa and 5 kDa) vs control hydrolyzed starch (26 KDa). 18 DEexperimental hydrolyzed starch demonstrated a slightly higher viscositycompared to that of control hydrolyzed starch samples. This shows alesser shear thinning as a functional of shear rate and temperaturecompared to that of hydrolyzed starch control. 18 DE experimentalhydrolyzed starch formed opaque, milky white dispersions compared to theclear dispersions formed by the control hydrolyzed starch samples.

TABLE 18 18 DE COMMON HYDROLYZED STARCH % Abundance #5 P-1 EXP #10 (16.3#10 P-1 DP range (19.1 DE) DE) (18.0 DE) 1-5 20.35 0 19.03 6-9 24.839.59 36.57 10-19 37.44 65.51 9.29 20-45 10.68 17.73 6.22  46-125 1.453.88 11.09 126-280 1.92 1.28 9.92 281-600 2.21 1.61 4.56  601-1500 0.750.39 1.96 >1500 0.37 0 1.36 DE 19.1 16.3 18.0 Polydispersity 6 2 16 (Rz,nm) 13 20 39 Average M. Wt (Kda) 7 5 26

TABLE 19 EXP #10 EXP # 5 P-1 #10 P-1 (19.1 DE) (16.3 DE) (18.0 DE) GelFormation NO — NO Gel Strength (g) (30% solids) 0 — 0 Gel Strength (g)(50% solids) Not — Not measured measured Viscosity (cp) at 95 C. at 200s⁻¹ 3.2 2.35 2.3 Viscosity (cp) at 50 C. at 200 s⁻¹ 6.6 5.38 4.5Viscosity (cp) at 20 C. at 1000 s⁻¹ 12.9 11.66 11.6 Viscosity (cp) at 20C. at 100 s⁻¹ 19.2 10.1 10.7 Clarity Opaque Opaque Clear L*a*b* HunterColor L* 70.32 — L* 34.97 a* −3.06 a* −2.43 b* 5.15 b* −0.43

Results: 1 DE Pea Starch-Based Hydrolyzed Starch

Tables 20 and 21 demonstrate the analytical properties of low DE Peastarch based hydrolyzed starches, targeting DE of 0 to 3. Table 22 showsEXP#31 Pea hydrolyzed starch forming stronger gel (as suggested by “toostiff to measure”) compared to both Exp#2, a Maxamyl® HT Ultra basedhydrolyzed starch and Exp#29, a control GC 100 based hydrolyzed starch(referred earlier in Table 13). A stronger gel formation suggests thatthe pea starch-derived hydrolyzed starch has a different compositionthan the common corn starch after treatment with Maxamyl® HT Ultra. Thestronger gel formation may allow cost savings because less product wouldbe needed to obtain similar thickening or gelling textures. Such peastarch-based maltodetxrins may also have potential to function as novelbinder and texturing for use in bakery for retaining moisture and inconfectionary-soft candies and gummies for gelatin replacement and shaperetention.

TABLE 20 Pea Hydrolyzed starch 1-2 DE % Abundance EXP # 32 EXP #31(GC100) DP range (0.55 DE) (2.19 DE) 1-5 0 0 6-9 0 0 10-19 0 0 20-45 03.22  46-125 0 30.46 126-280 0 10.99 281-600 27.14 6.81  601-1500 20.439.2 >1500 52.43 39.31 DE 0.55 2.19 Polydispersity 9 26 (Mw/Mn) Radius ofGyration 39 31 (Rz, nm) Av M. Wt (Kda) 1607 714

TABLE 21 0-3 DE Pea Hydrolyzed starch EXP # 32 EXP #31 (GC100) (0.55 DE)(2.19 DE) Gel Formation YES YES Gel Strength (g) — — (30% solids) GelStrength (g) — — (50% solids) Viscosity (cp) at TOO STIFF of a 957 95 C.at 200 s⁻¹ PASTE to measure Viscosity (cp) at viscosity at 30% 3580 50C. at 200 s⁻¹ d.s. Viscosity (cp) at 3600 20 C. at 1000 s⁻¹ Viscosity(cp) at 20 C. 18400 at 100 s⁻¹ Clarity Opaque Opaque L* of L*a*b* — —

Example 5: Dairy Applications of Experimental Hydrolyzed StarchPrototypes

A. Sour Cream Application Testing

The formulations used for making full fat (15% fat) and light fat (9%fat) sour cream are listed Table 22 and 23, respectively. In full fatsour creams, a Cargill Texturizing Solution's functional stabilizersystem, Vitex ASC 317, was used as base stabilizer. For light fat sourcream, Vitex ASC 208 was used as a stabilizer. For these trials, thecurrent modified food starch present in the Vitex stabilizer systems wasreplaced 100% with the hydrolyzed starch as specified in the formulationTables 22 and 23.

TABLE 22 Full Fat Sour Cream Formulation Control 1 Control DE Commonstabilizer Experimental 1 corn (VITEX DE Common hydrolyzed ASC Cornhydrolyzed starch 317) starch (EXP# 1) (EXP# 28) Ingredient % % % Rawcream 36% B.F. 45.60 45.60 45.60 Whole Milk 49.98 49.98 49.98 Non-fatdried milk 2.00 2.00 2.00 Whey Powder 0.78 0.78 0.78 Stabilizer (ASC317) 1.560 0.000 0.000 Stabilizer (ASC 317-replace 0.000 1.560 0.000starch with EXP#1 Stabilizer (ASC 317-replace 0.000 0.000 1.560 starchwith EXP#28 Sodium Citrate 0.050 0.050 0.050 Potassium Sorbate 0.0300.030 0.030

TABLE 23 Light Sour Cream Formulation Control 1 Control DE Commonstabilizer Experimental 1 corn (VITEX DE Common hydrolyzed ASC Cornhydrolyzed starch 208) starch (EXP# 1) (EXP# 28) Ingredient % % % Rawcream 36% B.F. 18 18 18 Whole Milk 76.63 76.63 76.63 Non-fat dried milk2.00 2.00 2.00 Stabilizer (ASC 208) 3.340 0.000 0.000 Stabilizer (ASC208-replace 0.000 3.340 0.000 starch with EXP#1 Stabilizer (ASC208-replace 0.000 0.000 3.340 starch with EXP#28 Potassium Sorbate 0.0300.030 0.030

Manufacturing Method Used for Manufacturing Sour Cream (Same Process forFull Fat and Light)

1. Batch cold add all dry ingredients as listed in the formulation.

2. Preheat the batch vessel to 150° F.

3. Homogenize @ 2500 psi (2 stage)

4. Pasteurize (180° F. with 30 second hold)

5. Cool to 78° F.

6. Add culture Flay 672/overnight

7. Break at pH 4.6

8. Smooth (pump/screens)

9. Package and refrigerate

Results

Both the sour creams were manufactured with the intention of removingmodified food starch from the product. The 1DE common-starchexperimental hydrolyzed starch (EXP#1) was the most favorable productcompared to the control hydrolyzed starch, EXP#28. The full fat andlight fat sour creams made with the 1DE experimental hydrolyzed starchboth maintained good viscosity, structure, and a smooth, shinyappearance, similar to the original sour cream formulations. The 1DEcontrol hydrolyzed starch had weaker structure and lower viscosity.(Table 24).

TABLE 24 Viscosity comparison in control and experimental sour creamproduct Control 1 DE Experimental 1 DE Common Common hydrolyzedhydrolyzed starch Control starch (EXP#1) (EXP# 28) Full fat sour creamViscosity at 154, 000 119, 000 — Day 1 (cps) Viscosity 161,000 139, 000115, 000 Day 7 (cps) Consistency Good structure, Good structure, WeakerStructure smooth shiny smooth shiny appearance appearance Light fat sourcream Viscosity at 107, 000 132, 000 — Day 1 (cps) Viscosity 107, 000163, 000  49, 000 Day 7 (cps) Consistency Good structure, Goodstructure, Weaker Structure smooth shiny smooth shiny appearanceappearance

B. Yogurt Application Testing

The formulations for gelatin replacement in regular (2% fat) yogurt areshown in Table 25. A Cargill Texturizing Solutions Functional System,Vitex AYS 79K, was used as the basis for the stabilizer with all trials.In these trials, the current gelatin was replaced with hydrolyzed starchto meet 4.43% of the total formulation and the weight of the functionalsystem was adjusted accordingly.

TABLE 25 Yogurt formulation Experimental 1 Control 1 DE Common DE CommonCorn corn Experimental Control hydrolyzed hydrolyzed 1 DE Waxystabilizer starch (EXP# starch Corn (AYS 79K) 1) (EXP# 28) (EXP#5)Ingredient % % % % Skim Milk 57.7 57.7 57.7 57.7 Whole Milk 31.00 31.0031.00 31.00 Non-fat dried milk 2.50 2.50 2.50 2.50 Experimentalhydrolyzed 0.00 0.00 0.00 0.00 starch Stabilizer (AYS 79 K) 2.30 0.000.00 0.00 Stabilizer (AYS 79K- 0.000 2.30 0.000 0.000 replace starchwith EXP#1 Stabilizer (AYS 79K- 0.000 0.000 0.000 2.3 replace starchwith EXP#5 Stabilizer (AYS 79K- 0.000 0.000 2.30 0.000 replace starchwith EXP#28 Sugar 6.50 6.50 6.50 6.50 Potassium Sorbate 0.030 0.0300.030 0.030

Manufacturing Method Used to Make Yogurt:

-   1. Add non-fat dry milk, whey protein concentrate to milk phase (use    defoamer). Hydrate 10 minutes-   2. Add dry ingredients. Hydrate 10 minutes-   3. Preheat to 190° F.-   4. Homogenize 1000 psi (500 1^(st)/500 2^(nd)) 2 stage-   5. Cool to 105-108° F.-   6. Collect into stainless container-   7. Add culture/Break at pH 4.65-4.70-   8. Pump through cooling press to 55-60° F.-   9. Use hand mixer on speed setting High for 90 seconds-   10. Refrigerate and evaluate after 24 hours.

Results:

Yogurt was manufactured to replace gelatin with experimental hydrolyzedstarch in the product. The removal of gelatin expands yogurt into avegetarian option. The experimental hydrolyzed starch, EXP#1 showedacceptable results of texture and body in the yogurt, compared to thecontrol hydrolyzed starch, which resulted in too thin body andunacceptable texture (Table 26). EXP#5 produced a product that was toothin, so no further testing was performed. No adverse syneresis wasnoticed in any of the yogurts.

TABLE 26 Yogurt texture and viscosity results Control 1 DE Experimental1 DE Common corn Control Common Corn hydrolyzed stabilizer hydrolyzedstarch starch (AYS 79K) (EXP# 1) (EXP# 28) Yogurt Vitex AYS 79K-1005Gelatin Replacement, Hydrolyzed starch at 4.43% Viscosity 16, 240 15,488 6, 960 Day 1, cps Viscosity 17, 480 32, 240 6, 520 Day 7, cpsTexture and Good body Good body and texture, Too thin body, Body andtexture Hydrolyzed starch could Unacceptable be further reduced in thetexture formulation

We claim:
 1. A hydrolyzed starch composition derived from common starch,wherein the hydrolyzed starch has a dextrose equivalent (DE value) ofgreater than 0 to 3, a degree of polymerization (DP) between 601-6172of >40%, and an average molecular weight (mw) of <3500 kDa.
 2. Thehydrolyzed starch composition of claim 1 which has a viscosity of >1000cp at 95° C. at 200 s⁻¹.
 3. The hydrolyzed starch composition of claim1, wherein the hydrolyzed starch has a lower average molecular weightand/or a higher percentage of hydrolyzed starches with a DP between601-6172 than a hydrolyzed starch with a similar DE produced byhydrolyzing common starch with α-amylase GC100.
 4. The hydrolyzed starchcomposition of claim 1, wherein the starch is corn starch, potatostarch, tapioca starch, pea starch, legume starch, or rich starch. 5.The hydrolyzed starch composition of claim 1, wherein the common starchis common corn starch.
 6. A dairy composition comprising the hydrolyzedstarch composition of claim
 1. 7. A hydrolyzed starch compositionderived from common starch, wherein the hydrolyzed starch has a dextroseequivalent (DE value) of 3 to 8, a degree of polymerization (DP) between10-125 of >20%, and an average molecular weight (mw) of <300 kDa.
 8. Thehydrolyzed starch composition of claim 7, wherein the hydrolyzed starchhas a lower average molecular weight and/or a higher percentage ofhydrolyzed starches with a DP between 10-125 than a hydrolyzed starchwith a similar DE produced by hydrolyzing common starch with α-amylaseGC100.
 9. The hydrolyzed starch composition of claim 7, wherein thestarch is corn starch, potato starch, tapioca starch, pea starch, legumestarch, or rich starch.
 10. The hydrolyzed starch composition of claim7, wherein the common starch is common corn starch.
 11. A dairycomposition comprising the hydrolyzed starch composition of claim
 7. 12.A hydrolyzed starch composition derived from common starch, wherein thehydrolyzed starch has a dextrose equivalent (DE value) of 14 to 20 andan average molecular weight (mw) of <20 kDa.
 13. The hydrolyzed starchcomposition of claim 12, wherein the composition has an opaque clarityindicated by a Hunter L value of >50.
 14. The hydrolyzed starchcomposition of claim 12, wherein the starch is corn starch, potatostarch, tapioca starch, pea starch, legume starch, or rich starch. 15.The hydrolyzed starch composition of claim 12, wherein the common starchis common corn starch.
 16. A dairy composition comprising the hydrolyzedstarch composition of claim 12.